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      Hollow Fiber Supported Liquid Membrane Extraction Combined with HPLC-UV for Simultaneous Preconcentration and Determination of Urinary Hippuric Acid and Mandelic Acid

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          Abstract

          This work describes a new extraction method with hollow-fiber liquid-phase microextraction based on facilitated pH gradient transport for analyzing hippuric acid and mandelic acid in aqueous samples. The factors affecting the metabolites extraction were optimized as follows: the volume of sample solution was 10 mL with pH 2 containing 0.5 mol·L −1 sodium chloride, liquid membrane containing 1-octanol with 20% ( w/ v) tributyl phosphate as the carrier, the time of extraction was 150 min, and stirring rate was 500 rpm. The organic phase immobilized in the pores of a hollow fiber was back-extracted into 24 µL of a solution containing sodium carbonate with pH 11, which was placed inside the lumen of the fiber. Under optimized conditions, the high enrichment factors of 172 and 195 folds, detection limit of 0.007 and 0.009 µg·mL −1 were obtained. The relative standard deviation (RSD) (%) values for intra- and inter-day precisions were calculated at 2.5%–8.2% and 4.1%–10.7%, respectively. The proposed method was successfully applied to the analysis of these metabolites in real urine samples. The results indicated that hollow-fiber liquid-phase microextraction (HF-LPME) based on facilitated pH gradient transport can be used as a sensitive and effective method for the determination of mandelic acid and hippuric acid in urine specimens.

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          Hollow fiber-protected liquid-phase microextraction of triazine herbicides.

          A new microextraction technique termed hollow fiber-protected liquid-phase microextraction (LPME) was developed. Triazines were employed as model compounds to assess the extraction procedure and were determined by gas chromatography/mass spectrometry. Toluene functioned as both the extraction solvent and the impregnation solvent. Some important extraction parameters, such as effect of salt, agitation, pH, and exposure time were optimized. The new method provided good average enrichment factors of > 150 for eight analytes, good repeatability (RSDs or = 0.9995) for spiked deionized water samples. The limits of detection (LODs) were in the range of 0.007-0.063 microg/L (S/N = 3) under selected ion monitoring mode. In addition to enrichment, hollow fiber-protected LPME also served as a technique for sample cleanup because of the selectivity of the membrane, which prevented large molecules and extraneous materials, such as humic acids in solution, from being extracted. The utilization of this procedure in the extraction of a slurry sample (mixture of soil and water) also gave good precision (RSDs <5.00%, n = 3) and LODs (0.04-0.18 microg/L, S/N = 3). Finally, the comparison of the new method with the static solvent drop LPME and solid-phase microextraction was performed. The results demonstrated that hollow fiber-protected LPME was a fast, accurate, and stable sample pretreatment method that gave very good enrichment factors for the extraction of triazine herbicides from aqueous or slurry samples.
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            Direct determination of chlorophenols in environmental water samples by hollow fiber supported ionic liquid membrane extraction coupled with high-performance liquid chromatography.

            The 1-octyl-3-methylimidazolium hexafluorophosphate ([C8MIM][PF6]) ionic liquid was immobilized in the pores of a polypropylene hollow fiber for hollow fiber-protected liquid-phase microextraction. Analytes including 4-chlorophenol (4-CP), 3-chorophenol (3-CP), 2,4-dichlorophenol (2,4-DCP) and 2,4,6-trichlorophenol (2,4,6-TCP) were extracted into this ionic liquid membrane, and back extracted into 10microL sodium hydroxide acceptor solution in the lumen of the hollow fiber. Then, the acceptor solution was withdrawn into the high-performance liquid chromatography (HPLC) microsyringe connected to the hollow fiber, and directly injected into the HPLC system for analysis. Some parameters that might affect the extraction efficiency were optimized, and low detection limits (0.5microgL(-1) for 4-CP, 3-CP, DCP and 1.0microgL(-1) for TCP) were obtained. Good repeatability was achieved because of the stability of the hollow fiber-supported ionic liquid membrane. The proposed procedure was applied for direct determination of the four chlorophenols in some real water samples including groundwater, river water, wastewater and tap water. All of the four chlorophenols in these water samples were under the limits of determination, and the recoveries were in the range of 70.0-95.7% at 5microgL(-1) spiked level.
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              Application of hollow fiber-based liquid-phase microextraction (HF-LPME) for the determination of acidic pharmaceuticals in wastewaters.

              The presence of pharmaceuticals in the environment is a very important problem that requires analytical solutions. The wide variety of matrices and, usually, the low pharmaceuticals levels in the environmental samples requires high sensitive and selective analytical procedures. Wastewaters are one of the more important sources of environmental pollutants but they are very complex matrices that need clean-up procedures prior the analysis. Hollow fiber-based liquid-phase microextraction (HF-LPME) is a relatively new technique used in analytical chemistry for sample pre-treatment that offers high selectivity and sensitivity compared to most traditional extraction techniques. The low organic solvent consumption derived from the use of HF-LPME is according to the current trends to a "Green Chemistry", and Analytical Chemistry should follow these environmental good practices. This paper describes an extraction method using a polypropylene membrane supporting dihexyl ether (three-phase hollow fiber-based liquid-phase microextraction (HF-LPME)) for the direct analysis of three pharmaceuticals (salicylic acid (SAC), ibuprofen (IBU) and diclofenac (DIC)) in raw and treated wastewaters followed by a HPLC/MS-MS determination using a highly packed Pursuit XRs Ultra 2.8 microm C18 column that allows high resolution using low flow-rates and, simultaneously, short retention times. Detection limits were 20, 100 and 300 ng L(-1) for salicylic acid, diclofenac and ibuprofen, respectively. Copyright 2010 Elsevier B.V. All rights reserved.
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                Author and article information

                Contributors
                Role: Academic Editor
                Journal
                Membranes (Basel)
                Membranes (Basel)
                membranes
                Membranes
                MDPI
                2077-0375
                12 February 2017
                March 2017
                : 7
                : 1
                : 8
                Affiliations
                [1 ]Excellence Centre of Occupational Health, Research Center for Health Sciences, School of Public Health, Hamadan University of Medical Sciences, Hamadan 6517838736, Iran; bahrami@ 123456umsha.ac.ir (A.B.); fghorbani@ 123456umsha.ac.ir (F.G.S.)
                [2 ]Department of Occupational Health, School of Public Health, Arak University of Medical Sciences, Arak 3819693345, Iran
                [3 ]Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, Tehran 1411713116, Iran; yyamini@ 123456modares.ac.ir
                [4 ]Department of Biostatistics and Epidemiology, School of Public Health and Center of Health Research, Hamedan University of Medical Sciences, Hamedan 6517838736, Iran; moghimb@ 123456yahoo.com
                Author notes
                [* ]Correspondence: f.ghamari@ 123456umsha.ac.ir ; Tel.: +98-918-851-3190
                Article
                membranes-07-00008
                10.3390/membranes7010008
                5371969
                28208685
                024977bd-56aa-47b8-a648-d63e3031558b
                © 2017 by the authors.

                Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license ( http://creativecommons.org/licenses/by/4.0/).

                History
                : 26 December 2016
                : 10 February 2017
                Categories
                Article

                hippuric acid,mandelic acid,toluene and ethylbenzene metabolites,hf-lpme,facilitated ph gradient transport,hplc-uv

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